KR102284405B1 - Laminate body, barrier film, and manufacturing method of these - Google Patents

Abstract

A laminated body 1 includes a substrate 4 having a surface, a film or film undercoat layer 3 formed on at least a part of the surface of the substrate 4 and containing an organic polymer having an OH group; , a precursor as a raw material, and an atomic layer deposition film (2) formed in the form of a film covering the exposed surface of the undercoat layer (3), wherein at least a portion of the precursor is formed in the OH group of the organic polymer are combining

Description

Laminate, barrier film, and manufacturing method thereof

The present invention relates to a laminate, a barrier film, and a method for making the same.

This application claims priority based on Japanese Patent Application No. 2013-066165 for which it applied to Japan on March 27, 2013, and Japanese Patent Application No. 2013-267184 for which it applied to Japan on December 25, 2013 and the contents are cited here.

Methods of forming a thin film on the surface of an object using a vapor phase that makes a material move at an atomic/molecular level like gas are chemical vapor deposition (CVD) and physical vapor deposition (PVD: Physical Vapor Deposition).

Typical PVDs include a vacuum deposition method and a sputtering method. In particular, the sputtering method can form a high-quality thin film excellent in film quality and uniformity of film thickness, although the apparatus cost is generally high. Therefore, it is widely applied to a liquid crystal display, a display device, etc.

Further, CVD is a method of growing a solid thin film by introducing a source gas into a vacuum chamber and decomposing or reacting one or two or more types of gases on a substrate by thermal energy. When decomposing or reacting gas, in order to accelerate the reaction at the time of film-forming, or to lower|hang the reaction temperature, there is also a method of using plasma or a catalyst (Catalyst) reaction together, PECVD (Plasma Enhanced CVD), Cat-CVD, respectively. It is called etc. Such CVD is characterized by few film-forming defects, and is mainly applied to the manufacturing process of semiconductor devices, such as film-forming of a gate insulating film.

In addition, in recent years, an atomic layer deposition method (ALD method: Atomic Layer Deposition) is attracting attention. This ALD method is a method of depositing a surface-adsorbed substance into a film layer by layer at the atomic level by a chemical reaction on the surface, and is classified into the category of CVD. Also, what distinguishes the ALD method from general CVD is that so-called CVD (general CVD) is a method of growing a thin film by using a single gas or a plurality of gases at the same time to react on a substrate. In contrast, the ALD method alternately uses a precursor (TMA: Tri-Methyl Aluminum) or a gas rich in activity called a precursor and a reactive gas (this is also called a precursor in ALD), adsorption on the substrate surface, It is a special film-forming method in which a thin film is grown one by one at an atomic level by a chemical reaction following this.

However, as drawbacks of the ALD method, there is a need to use a special material in order to perform the ALD method and an increase in cost thereof. The biggest drawback is that the film formation speed is slow. For example, compared with a film-forming method, such as a normal vacuum vapor deposition or sputtering, the film-forming speed|rate is about 5 to 10 times slow.

In addition, in order to obtain a high-quality film by the ALD method, it is known that not only the process of the ALD method is improved, but also the entire process of the ALD method is similarly important (for example, refer to Patent Document 1). Patent document 1 is disclosing the technique which can improve the step coverage of the film|membrane by the following ALD method by performing plasma processing to the insulating layer on a semiconductor substrate.

Moreover, as a related art, the technique of forming a gas permeation barrier layer on a plastic substrate or a glass substrate by performing atomic layer deposition by ALD method is disclosed (for example, refer patent document 2). In Patent Document 2, a light-emitting polymer is mounted on a light-transmitting plastic substrate, and atomic layer deposition is performed on the surface and side surfaces of the light-emitting polymer by ALD (top coating). Thereby, while being able to reduce a coating defect, the technique of realizing the light-transmissive barrier film which can reduce gas permeation|transmission with an outstanding difference in the thickness of several tens of nanometers is disclosed.

Japanese Patent Publication No. 2008-532271 Japanese Patent Publication No. 2007-516347 Japanese Patent Laid-Open No. 2012-96431 International Publication No. 2013/015412

As described above, a laminate in which an atomic layer deposition film is provided on the outer surface of a substrate by the ALD method is widely known conventionally, and these laminates are preferably used for a gas barrier film having gas barrier properties and the like.

However, in the conventionally known laminate, the atomic layer deposition film is laminated on a polymer substrate, and the growth pattern thereof is highly likely to be different from the case in which inorganic crystals such as Si wafers are used as the substrate. When an oxidation-treated Si wafer is used as a substrate, precursor adsorption sites exist at a density approximately equal to that of a crystal lattice, and film growth proceeds in a two-dimensional growth mode. However, in the case of using a polymer substrate, since the distribution density of the adsorption sites of the precursor is low, the isolated and adsorbed precursor is used as a nucleus, and three-dimensional growth and expansion are carried out, so that the adjacent nuclei come into contact with each other to form a continuous film. In addition, it was found that, depending on the state of the substrate and the ALD process conditions, there is a high possibility that the film is growing in a columnar shape from the outer surface of the substrate to a direction perpendicular to the outer surface of the substrate. That is, in the conventional laminate, since a plurality of columnar structures are arranged and formed on a base material, there is a risk that gas enters and exits through gaps between the columnar structures. In other words, there exists a possibility that the said conventional laminated body does not have ideal gas-barrier property.

In addition, when there is no ideal adsorption site on the polymer substrate, there is a fear that a laminate cannot be formed on the polymer substrate by using the ALD method.

Patent Document 4 discloses a method of introducing an undercoat layer on the polymer substrate and introducing highly reactive nucleophilic groups at a high density. However, since this method is performed offline, there exists a possibility that the functional group with high reactivity on the surface reacts with the substance in air|atmosphere, and there exists a possibility that it may deactivate, and there exists a possibility that the surface of an undercoat layer may become contaminated.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a laminate with high gas barrier properties.

In order to solve the said subject, this invention employ|adopted the following structures.

The laminate according to the first aspect of the present invention comprises a substrate having a surface, a film or film undercoat layer formed on at least a part of the surface of the substrate and containing an organic polymer having an OH group, and a precursor as a raw material. and an atomic layer deposition film formed in the form of a film that covers the exposed surface of the undercoat layer. Moreover, at least a part of the said precursor is couple|bonded with the said OH group of the said organic polymer.

Moreover, the copolymer of poly(methacrylic acid-2-hydroxyethyl) and polymethyl methacrylate may be sufficient as the said organic polymer.

Moreover, the copolymer in which the poly(methacrylic acid-2-hydroxyethyl) of the said copolymer is contained in the ratio of 15 mol% or more and 50 mol% or less in a copolymer may be sufficient.

In addition, a part of the OH groups in the poly(methacrylic acid-2-hydroxyethyl) may be crosslinked to form a three-dimensional network structure.

A laminate according to a second aspect of the present invention includes a polymer substrate having a surface, a film or film undercoat layer formed on at least a part of the surface of the polymer substrate and containing an organic polymer, and the undercoat It is formed so as to cover the surface of the layer, contains a nucleophilic functional group, and at least one of the element ratio O/C of the oxygen element O and the carbon element C and the element ratio N/C of the nitrogen element N and the carbon element C is the undercoat An adhesion layer larger than the layer is provided, and an atomic layer deposition film formed so as to cover the surface of the adhesion layer using a precursor as a raw material. Moreover, at least a part of the said precursor is couple|bonded with the said nucleophilic functional group.

Moreover, the said undercoat layer may have the element or functional group containing a lone pair.

Moreover, the film thickness of the said contact bonding layer may be 0.1 nm or more and 100 nm or less.

Moreover, 100 nm or more and 100 micrometers or less may be sufficient as the film thickness of the said undercoat layer.

Further, the thickness of the atomic deposition film may be 2 nm or more and 50 nm or less.

Further, the atomic layer deposition film may contain at least one of Al and Si.

Further, Ti may be included on the surface of the atomic deposition film in contact with the adhesion layer.

Moreover, the gas barrier film which concerns on the 3rd aspect of this invention contains the laminated body of the said aspect formed in the film form.

Moreover, in the manufacturing method of the laminated body which concerns on the 4th aspect of this invention, a base material is prepared, and at least a part of the surface of the said base material forms a film|membrane or film type undercoat layer containing the organic polymer which has a functional group, , a part of the exposed surface of the undercoat layer is surface-treated to densify the functional groups of the organic polymer, and the precursor to be an atomic layer deposition film contains OH groups and the densified functional groups of the organic polymer contained in the undercoat layer supplying a precursor raw material on the exposed surface to bind to, removing an excess precursor raw material that is not bound to the undercoat layer among the precursor raw materials, and OH groups of the organic polymer and the functional groups of the densified organic polymer By saturating the amount of binding of the precursor to the atomic layer, an atomic layer deposition film is formed.

Further, in the method for producing a laminate according to a fifth aspect of the present invention, a substrate is prepared, and a film-like or film-like undercoat layer containing an organic polymer having a functional group is formed on at least a part of the surface of the substrate, , an adhesive layer having a nucleophilic functional group is formed on the undercoat layer by surface treatment of at least a part of the exposed surface of the undercoat layer, and the precursor used as the atomic layer deposition film is a functional group of the undercoat layer or the adhesive layer In order to bind to the nucleophilic functional group of The amount of the precursor bound to the functional group or the nucleophilic functional group of the adhesion layer is saturated to form an atomic layer deposition film.

Moreover, in the manufacturing method of the gas barrier film which concerns on the 6th aspect of this invention, the laminated body manufactured by the laminated body manufacturing method of the said aspect forms in film form.

According to the above aspect of the present invention, even in the atomic layer deposition method based on a polymer, the adsorption sites of the precursor can be arranged at a high density by the undercoat layer containing the organic polymer having an OH group, and atoms close to two-dimensional growth layer growth is possible.

Further, according to the above aspect of the present invention, even in the atomic layer deposition method based on a polymer, the atomic layer deposition film is two-dimensional by the undercoat layer having a highly reactive functional group and the adhesive layer having more highly reactive functional groups. Atomic layer growth close to growth becomes possible.

Further, according to the above aspect of the present invention, since the two-dimensional atomic layer deposition film is a film in which atoms are densely bonded in the plane direction, there are few gaps through which gas passes in the film thickness direction. Therefore, the gas barrier property of a laminated body or a gas barrier film can be made higher.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the structure of the laminated body which concerns on 1st Embodiment of this invention.
2A is a diagram showing the chemical formula of a methyl group, which is a polymer material constituting the substrate according to the first and second embodiments of the present invention.
2B is a diagram showing the chemical formula of an ester group, which is a polymer material constituting the substrate according to the first and second embodiments of the present invention.
3 is a diagram showing the chemical formula of an organic polymer including an OH group.
It is sectional drawing which shows the structure of the laminated body which concerns on 2nd Embodiment of this invention.
5 is a diagram showing the chemical formula of an undercoat layer according to a second embodiment of the present invention.
6 is a view showing the chemical formula of the undercoat layer 3 according to the embodiment of the present invention.
7 is a view comparing the water vapor transmission rate of the laminate of this example having a UC layer containing an OH group and a laminate of _{a comparative example having a UC layer containing a CH 3 group.}

[First embodiment]

A first embodiment of the present invention will be described below.

<Configuration of the laminate according to the first embodiment>

First, the structure of the laminated body which concerns on 1st Embodiment of this invention is demonstrated. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the structure of the laminated body which concerns on embodiment of this invention. As shown in FIG. 1 , the laminate 1 includes a substrate 4 formed of a polymer material, and a film or film undercoat layer formed on the surface of the substrate 4 (hereinafter referred to as “UC layer”). (3) and an atomic layer deposition film (hereinafter referred to as "ALD film") formed on the surface (on the surface of the UC layer 3) opposite to the surface in contact with the substrate 4 among both surfaces of the UC layer 3 in the thickness direction (2) is provided. Moreover, the UC layer 3 contains the organic polymer which has an OH group, and the adsorption site of the ALD film|membrane 2 is ensured. That is, the organic polymer contained in the UC layer 3 has a functional group to which the precursor of the ALD film 2 is easily adsorbed. Accordingly, when the precursor, which is a raw material of the ALD film 2 , bonds to the OH group of the organic polymer contained in the UC layer 3 , the ALD film 2 is formed in a film shape so as to cover the UC layer 3 .

The base material 4 formed of a polymer material is demonstrated. 2A and 2B are diagrams showing the functional group chemical formula of the polymer material constituting the substrate 4 .

As shown in FIG. 2A , when polypropylene (PP) having a methyl group and not having a polar group such as an OH group is used for the substrate, the initial growth of the amount of the ALD film (ie, the adsorption rate of the precursor) is Al ₂ It _{is slower than O 3} (alumina). In other words, when PP is used as the substrate, the precursor is hardly adsorbed because the functional group is a methyl group. Therefore, PP is not preferable as a polymer material used for the substrate.

On the other hand, as shown in FIG. 2B , when polyethylene terephthalate (PET) having a polar group such as an ester group is used for the substrate, the initial growth of the film formation amount of the ALD film (that is, the adsorption rate of the precursor) is Al ₂ O ₃ (alumina) faster than In other words, when PET is used as the substrate, the precursor is easily adsorbed because the functional group is an ester group. Therefore, PET is preferable as the polymer material used for the substrate.

That is, it is not preferable to use PP or the like having a methyl group to which the precursor is hardly adsorbed for the substrate 4 . On the other hand, it is preferable to use PET having an ester group to which the precursor is easily adsorbed for the substrate 4 . That is, the polarity of the functional group and the presence or absence of an atom providing electrons greatly affect the adsorption rate of the precursor. Therefore, when a polymer material such as PP is used for the substrate 4 , it is difficult to directly form the ALD film 2 on the substrate 4 . Therefore, in that case, it is preferable to provide the UC layer 3 on the base material 4, and to provide the ALD film|membrane 2 on it.

When the UC layer 3 is formed on the substrate 4 , the ALD film 2 can be formed densely, so the material of the substrate 4 is polyethylene (PE), polypropylene (PP) or polystyrene. You may use a polymer material only for hydrocarbons, such as (PS). Of course, even when the UC layer 3 is formed on the substrate 4, a polymer material containing O atoms such as polyethylene terephthalate (PET), N atoms such as nylon, or S atoms such as polyether sulfone is used. do.

The organic polymer which is contained in the UC layer 3 and which has an OH group which the ALD film|membrane 2 is easy to adsorb|suck is demonstrated. 3 is a diagram showing the structural formula of an organic polymer having an OH group. When polyvinyl alcohol (PVA) shown in FIG. 3 is used as the organic polymer contained in the UC layer 3 , the initial growth of the film formation amount of the ALD film (that is, the adsorption rate of the precursor) is fast. In other words, when PVA is used as the material of the organic polymer of the UC layer 3, since the functional group is a hydroxyl group, the precursor is slightly adsorbed. Therefore, PVA is preferable as an organic polymer material used for the UC layer 3 .

Examples of the organic polymer having an OH group preferable as the UC layer 3 include polyvinyl alcohol shown in FIG. 3 , phenol resins, polysaccharides, and the like. Further, specific examples of the polysaccharide include cellulose derivatives such as cellulose, hydroxymethylcellulose, hydroxyethylcellulose and carboxymethylcellulose, chitin and chitosan. In addition, as a material of the UC layer 3, you may use the copolymer of the said organic polymer and another organic polymer, or the hybrid material of the said organic polymer and an inorganic substance.

Moreover, although an epoxy resin which has an OH group, an acrylic resin, etc. are mentioned as another material of the UC layer 3, Especially, the air of poly(methacrylic acid-2-hydroxyethyl) and polymethyl methacrylate It is more preferable to use a coalescence. At this time, when poly(methacrylic acid-2-hydroxyethyl) is contained in a proportion of 15 mol% or more and 50 mol% or less in the copolymer, the amount of adsorption sites is sufficient and coating can be performed using various solvents. .

Moreover, it is preferable that the organic polymer which has an OH group contained in the UC layer 3 is bridge|crosslinked in a molecule|numerator. Thereby, since the three-dimensional meshwork structure is formed in the UC layer 3, the wet-and-heat tolerance of the laminated body 1 improves. As a material which crosslinks the inside of the molecule|numerator of the organic polymer which has an OH group, organic polymers containing NCO groups, such as Sumidur N3300 (made by Sumika Bayer Urethane Co., Ltd.), are mentioned. By adding an organic polymer containing an NCO group, an intermolecular crosslinking reaction occurs by reacting the NCO group with at least a part of the OH group in the UC layer 3 . By forming the three-dimensional mesh structure in the UC layer 3 in this way, the wet heat resistance of the laminate 1 is improved.

The ALD film 2 may be _{an inorganic oxide film such as AlO x} , TiO _x , SiO _x , ZnO _x or SnO _x , a nitride film or an oxynitride film containing these inorganic substances, or an oxide film, a nitride film, or an oxynitride film containing other elements. In addition, the ALD film 2 may be the above-mentioned film or a mixed film of elements.

In the laminate 1 including the substrate 4, the UC layer 3 and the ALD film 2, the precursor, which is a raw material of the ALD film 2, can be arranged at a high density at the adsorption site of the UC layer 3, , atomic layer growth of the ALD film 2 close to two-dimensional growth becomes possible. The two-dimensional ALD film 2 is a film in which atoms are densely bonded in the plane direction. Therefore, there are few gaps through which gas permeate|transmits in the film thickness direction, and gas barrier property can be made higher. Therefore, by forming the laminate 1 in a film form, it can be used as a gas barrier film.

<The manufacturing method of the laminated body which concerns on 1st Embodiment>

Next, the manufacturing method of the laminated body which concerns on 1st Embodiment of this invention is demonstrated. First, the base material 4 containing a polymer material is loaded in the vacuum chamber of an ALD apparatus (1st process). Next, a film-like or film-like UC layer 3 containing an organic polymer having an OH group is formed on at least a part of the outer surface (surface) of the substrate 4 (second step). Next, among both surfaces in the thickness direction of the UC layer 3 formed in the second step, a part of the surface (exposed surface of the UC layer 3) on the opposite side to the surface in contact with the base material 4 is surface-treated, and the UC layer ( The functional group of the organic polymer contained in 3) is densified (third step). Next, among both surfaces in the thickness direction of the UC layer 3, so that the precursor, which is a raw material for the atomic layer deposition film, binds to the OH group of the organic polymer contained in the UC layer 3 and the functional group of the organic polymer that has been densified in the third step. , A precursor raw material is supplied on the surface (exposed surface of the UC layer 3) opposite to the surface in contact with the substrate 4 (fourth step). Finally, in the fourth step, the surplus precursor raw material that has not been bound is removed, the amount of binding of the precursor bound to the OH group of the organic polymer and the functional group of the organic polymer that has been densified in the third step is saturated to saturate the atomic layer deposition film is formed (fifth step).

A 2nd process WHEREIN: The method of forming the UC layer 3 is not specifically limited, A suitable coating technique, such as a spin coating method, a roll coating method, or a bar coating method, can be used.

3rd process WHEREIN: As a method of surface-treating a part of UC layer 3, plasma processing (plasma etching), alkali treatment, etc. are mentioned. Thereby, OH groups and COOH groups appear in a part of the surface of the UC layer 3, and a functional group is densified. As a result, the density at which the precursor, which is a raw material for the ALD film 2 formed in the fourth and fifth steps, cross-links to the functional group of the UC layer increases. Thus, gas barrier property can be made still higher by making the functional group of the organic polymer contained in the UC layer 3 high density.

In the fourth and fifth steps, an atomic layer deposition method (ALD method) is used as a method for forming the ALD film 2 . A precursor raw material (source gas) is supplied, and a purge gas is supplied to remove excess precursor material. Moreover, it is considered that a precursor and some adsorption site are not couple|bonded only by supplying and removing a precursor raw material once. Accordingly, the ALD film 2 is formed by repeating the step of supplying the precursor raw material and the step of evacuating and removing the surplus precursor raw material to saturate the bonding amount of the precursor to the OH group and the functional group of the organic polymer. It is preferable that the frequency|count of supply and exhaustion of a precursor raw material is 1 or more and 30 or less times.

[Second embodiment]

A second embodiment of the present invention will be described below.

<Summary of the second embodiment>

The laminate according to the second embodiment of the present invention has an undercoat layer and an adhesion layer between the substrate and the atomic layer deposition film. This undercoat layer is a layer containing an organic polymer, and the organic polymer has a bonding site to which the precursor of the atomic layer deposition film binds. That is, the organic polymer contained in the undercoat layer has a large number of functional groups as bonding sites that are easy to bond with the precursor of the atomic layer deposition film. Further, the adhesion layer is a layer provided on the surface layer of the undercoat layer, and is a bonding site that is easily bonded to the precursor of the atomic layer deposition film, and has many more functional groups. Accordingly, the precursors bonded to each functional group of the undercoat layer or the adhesion layer are bonded to each other so as to crosslink each other. Thereby, a two-dimensional atomic layer deposition film that grows in the plane direction of the adhesion layer is formed. As a result, it becomes difficult to generate the gap through which gas permeates in the film thickness direction of a laminated body, and a laminated body with high gas-barrier property can be implement|achieved. In addition, an inorganic substance may be disperse|distributed to the undercoat layer. That is, by adding an inorganic substance to the undercoat layer, the precursor adsorption density of the atomic layer deposition film can be further improved.

A laminate having an atomic layer deposition film manufactured by the atomic layer deposition method (ALD method) is commercially produced as a substrate for electronic components such as a glass substrate or a silicon substrate, such as thin-film wireless EL, display, semiconductor memory (DRAM), etc. is losing On the other hand, as for the base material of the laminated body used as the object of 2nd Embodiment, the polymer base material which has flexibility is an object. However, under the present circumstances, the process of the ALD method for a polymer substrate has not been studied in detail. Therefore, in this study, it was assumed that the atomic layer deposition film grows on the polymer substrate as in the case of the electronic component substrate. Then, while considering the growth process of the atomic layer deposition film on the polymer substrate, an approach to the laminate of the second embodiment was attempted.

In general, it is thought that an atomic layer deposition film on an electronic component substrate grows two-dimensionally, but in reality, an atomic layer deposition film on a polymer substrate (eg, PET: polyethylene terephthalate) does not grow two-dimensionally. In other words, when a thin film of an atomic layer deposition film is formed on a polymer substrate by an ALD process, there is a fear that desired two-dimensional growth is not achieved.

It is thought that the main causes are the "density of adsorption sites" and "arrangement of adsorption sites" on the polymer substrate. For this reason, since the performance of the atomic layer deposition film cannot be sufficiently exhibited with a thin film thickness, the atomic layer deposition film needs to have a thickness of 2 nm or more or a number of atomic layers of 20 or more. Further, if the polymer substrate has a columnar structure, a complete gas barrier cannot be realized because gas permeates from the boundary portion of the columnar structure.

The density of precursor adsorption sites in the atomic layer deposition film, which is the first cause, is considered as follows. That is, the first step of the ALD process is that a gaseous precursor (TMA: Tri-Methyl Aluminum) or _{a metal-containing precursor such as TiCL 4} is chemically adsorbed onto the surface of a polymer substrate (hereinafter, sometimes simply referred to as a substrate). 1 step. At this time, the reactivity of the functional groups of the precursor and the substrate and the density of the functional groups greatly affect the chemical adsorption.

For example, in the case of a polymer (polymer), the precursor in the atomic layer deposition film is adsorbed to the adsorption site reversibly as shown in the following formula (1).

That is, in the formula (1), the OH group present in the polymer chain is adsorbed to the adsorption site.

The precursor of the atomic layer deposition film can be adsorbed to a functional group such as OH and COOH groups of a polymer chain, but is hardly adsorbed to a non-polar functional group such as an alkyl group.

Moreover, when the density of functional groups is low, each adsorption site of a precursor is arrange|positioned in the isolated state. In this way, when the adsorption sites are arranged in an isolated state, the growth of the atomic layer deposition film is three-dimensionally grown with the adsorption site as a nucleus. That is, when the density of the adsorption site is low, the atomic layer deposition film expands three-dimensionally in the precursor, and the precursor is sparsely adsorbed at locations such as OH. As a result, the atomic layer deposition film grows in a columnar shape centered on the isolated nucleus.

Next, the arrangement of the adsorption site (that is, diffusion of the precursor) as the second cause is considered as follows. In general, in a polymer film, a crystalline region and an amorphous region are mixed. Therefore, in the amorphous region, there is a space called a free volume (free volume) in which the polymer chain does not exist, and the gas diffuses and permeates through the space. Further, the gaseous precursor also permeates through the space of the free volume until it is adsorbed to the adsorption site.

For the above reasons, in the process of the ALD method for a polymer substrate, the precursor diffuses from the surface of the polymer substrate to the inside and is adsorbed to adsorption sites of functional groups scattered three-dimensionally, and the adsorption sites are atomic It becomes the nucleus of the layer deposition film. Since these nuclei are interspersed three-dimensionally, a three-dimensional growth mode occurs until a certain nucleus comes into contact with adjacent nuclei to form a continuous film. Therefore, since the period from when the atomic layer deposition film becomes a continuous film until the formation of a dense film by two-dimensional growth starts is long, the dense portion of the two-dimensional growth of the atomic layer deposition film decreases. As a result, the gas passes through the gaps in the atomic layer deposition film. Furthermore, the gas passes through the space of the free volume. Therefore, a high degree of gas barrier property is not obtained in the laminate.

Therefore, in the second embodiment of the present invention, in order to realize two points: (1) increasing the density of the adsorption sites of the precursor, and (2) preventing the diffusion of the precursor into the polymer substrate, the organic substrate on the polymer substrate An undercoat layer containing a polymer is provided, and an adhesion layer having more adsorption sites is formed on this undercoat layer. That is, in order to two-dimensionally arrange the adsorption sites of the precursor on the surface of the polymer substrate at high density, an undercoat layer containing an organic polymer is provided on the polymer substrate before the ALD process, and also on the surface of the undercoat layer. to form an adhesive layer. In addition, in order to further increase the density of the adsorption site of a precursor, you may add an inorganic substance to an undercoat layer. In this way, by forming the undercoat layer containing the organic polymer on the polymer substrate, the gas containing the precursor cannot pass through the undercoat layer.

<Configuration of the laminate according to the second embodiment>

First, the structure of the laminated body which concerns on 2nd Embodiment of this invention is demonstrated.

4 : is sectional drawing which shows the structure of the laminated body 11 which concerns on 2nd Embodiment of this invention. As shown in FIG. 4 , the laminate 11 includes a substrate (polymer substrate) 14 formed of a polymer material, and a film-type or film-type undercoat layer (hereinafter referred to as “UC layer”) formed on the surface of the substrate 14 . 13), an adhesion layer 15 formed on the surface (exposed surface) of the UC layer 13, and an atomic layer deposition film formed on the surface of the adhesion layer 15 (hereinafter referred to as "ALD film") ) (12) is provided. Further, the UC layer 13 contains an organic polymer material and has a precursor adsorption site for the ALD film 12 . Further, the adhesion layer 15 is almost the same compound as the UC layer 13, and at least one of the element ratio O/C of the oxygen element O and the carbon element C and the element ratio N/C of the nitrogen element N and the carbon element C is There are more adsorption sites for the ALD film 12 than for the UC layer 13 , and more sites for adsorption of the ALD film 12 than for the UC layer 13 are secured. That is, the compound constituting the adhesion layer 15 has many functional groups to which the precursor of the ALD film 12 is easily adsorbed. Accordingly, when the precursor, which is a raw material of the ALD film 12 , is combined with a functional group containing an O element or an N element contained in the adhesion layer 15 , the ALD film 12 is UC through the adhesion layer 15 . It is formed in a film shape so as to cover the layer 13 .

(write)

As the substrate (polymer substrate) 14 , the ALD film 12 can be densely formed by forming the UC layer 13 and the adhesion layer 15 . Therefore, you may use only hydrocarbon polymeric materials, such as polyethylene (PE), polypropylene (PP) which has a methyl group lacking in nucleophilicity (refer FIG. 2A), and polystyrene (PS). In addition, as a material of the base material 14, O atoms such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) having a nucleophilic ester group (refer to FIG. 2B), N such as nylon and polyimide (PI) A polymer material containing atoms and S atoms such as polyether sulfone may be used.

The film thickness of the base material 14 will not be specifically limited if it is the thickness which can be used as a barrier film. As a film thickness of the base material 14, specifically, for example, the range of 12-300 micrometers is preferable, and the range of 50-100 micrometers is more preferable.

(UC floor)

As the UC layer 13, it is preferable that it is an organic polymer. In addition, an inorganic substance or a hybrid material of an organic polymer and an inorganic substance may be used. As for the organic polymer preferable as the UC layer 13, organic polymers, such as polyvinyl alcohol which has an OH group, and a phenol resin, polysaccharide, etc. are mentioned, for example.

Moreover, as the UC layer 13, it is preferable to have the element or functional group containing a lone pair. It is preferable that the functional group of the organic polymer contained in the UC layer 13 has one of an O atom and an N atom. Examples of the functional group having an O atom include OH group, COOH group, COOR group, COR group, NCO group or SO ₃ group. Moreover, as for the functional group which has an N atom, NH _x group (X is an integer) is mentioned. The functional group of the organic polymer contained in the UC layer includes, in addition to the above, atoms having a lone pair of electrons or unpaired electrons (dangling bonds), and coordination bonds with precursors, bonds by intermolecular forces (van der Waals forces), hydrogen bonds, etc. It may also be a functional contribution to the interaction of

Further, it is possible to form an undercoat having a desired density of functional groups by surface-treating the organic polymer surface by plasma etching or hydrolysis treatment to increase the density of the functional groups of the organic polymer. Specifically, an organic polymer having an aromatic ring, such as polyphenylsulfone (PPS), is preferable, and for example, an organic polymer in which an aromatic ring is ring-opened by plasma etching or the like to form an OH group or a COOH group is preferable.

Further, as the organic polymer having an OH group, specifically, for example, an epoxy resin or an acrylic resin is preferable, and among them, poly(methacrylic acid-2-hydroxyethyl) and polymethyl methacrylate It is more preferable to use a copolymer (see Fig. 5). At this time, when poly(methacrylic acid-2-hydroxyethyl) is contained in a proportion of 15 mol% or more and 50 mol% or less in the copolymer, the amount of adsorption site is sufficient and it is preferable because it can be coated with various solvents. .

Specific examples of the polysaccharide include cellulose derivatives such as cellulose, hydroxymethylcellulose, hydroxyethylcellulose and carboxymethylcellulose, chitin, and chitosan.

Moreover, as the UC layer 13, you may use the organic polymer which has COOH group which is a nucleophilic functional group, an ester bond, an N atom, or an S atom, for example. Further, as the UC layer 13, a copolymer of an organic polymer and another organic polymer or a hybrid material of an organic polymer and an inorganic substance may be used.

In addition, although the film thickness of the UC layer 13 is not specifically limited, It is preferable that they are 100 nm or more and 100 micrometers or less. If the film thickness of the UC layer 13 is less than 100 nm, since a location where the UC layer cannot be formed due to uneven coating or the like occurs, it is not preferable. On the other hand, when the film thickness exceeds 100 µm, the substrate is distorted due to the shrinkage of the UC layer 13, which is not preferable. On the other hand, if the film thickness of the UC layer 13 is in the said range, since the UC layer can be apply|coated uniformly and the influence of shrinkage can be suppressed, it is preferable.

(Organic polymer used for UC layer)

Next, the organic polymer used for the UC layer 13 is demonstrated. Organic polymers are classified into aqueous and solvent based on the solvent used. As an aqueous organic polymer, polyvinyl alcohol, polyethyleneimine, etc. are mentioned. Moreover, acrylic ester, polyether acryl, polyether acryl, etc. are mentioned as solvent-type organic polymer|macromolecule.

Next, a more detailed specific example of the organic polymer used for the UC layer 13 will be described.

1. Organic polymer of zero atom containing resin

As a material preferable as an organic polymer of an O atom containing resin, polyvinyl alcohol, a phenol resin, polysaccharide, etc. which are hydroxyl group (OH) containing resin are mentioned. Moreover, cellulose derivatives, such as a cellulose, hydroxymethylcellulose, hydroxyethyl cellulose, and carboxymethylcellulose, chitin, chitosan, etc. are contained in polysaccharide.

Moreover, as a material preferable as an organic polymer of O atom containing resin, the carboxyvinyl polymer etc. which are carbonyl group (COOH) containing resin are mentioned.

Examples of other organic polymers of the O atom-containing resin include polyketone, polyetherketone, polyetheretherketone, and aliphatic polyketone, which are ketone group (CO)-containing resins. Examples of other organic polymers of the O atom-containing resin include polyester resins, polycarbonate resins, liquid crystal polymers, polyethylene terephthalate (PET), and polybutylene terephthalate (PBT), which are ester group (COO)-containing resins. , polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polytrimethylene terephthalate (PTT). In addition, you may use the epoxy resin or acrylic resin etc. which contain the said functional group.

2. Organic polymers of N-atom-containing resins

Preferred materials for the organic polymer of the N-atom-containing resin include polyimide, polyetherimide, alicyclic polyimide, and solvent-soluble polyimide, which are imide group (CONHCO)-containing resins. In addition, about an alicyclic polyimide, the aromatic polyimide which comprises an alicyclic polyimide is usually obtained from aromatic tetracarboxylic dianhydride and aromatic diamine. However, the alicyclic polyimide obtained from these materials is not transparent. Accordingly, as for the transparency of the polyimide, it is also possible to replace the acid dianhydride and diamine in the above materials with aliphatic or alicyclic, respectively. Examples of the alicyclic carboxylic acid include 1,2,4,5-cyclohexanetetracarboxylic acid and 1,2,4,5-cyclopentanetetracarboxylic dianhydride. Examples of the solvent-soluble polyimide include γ-butyrolactone, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

3. Organic Polymers of S-Atom-Containing Resins

Examples of the material that can be used as the organic polymer of the S atom-containing resin include polyether sulfone (PES), polysulfone (PSF) and polyphenyl sulfone (PPS), which are _{sulfonyl group (SO 2 )-containing resins.} Among them, PES and PSF are materials with high heat resistance. Polymer alloy, polybutylene terephthalate-based polymer alloy, polyphenylene sulfide-based polymer alloy and the like can also be used as the organic polymer. In addition, if necessary, the polymer may be composited with a polymer alloy (alloy, blend, composite).

Moreover, in the laminated body which concerns on embodiment of this invention, when using the organic polymer of O atom containing resin for the UC layer 13, since the effect obtained by the adhesion layer 15 becomes especially remarkable, it is preferable.

(Inorganic material added to UC layer)

As described above, when an inorganic material (inorganic compound) is added to the UC layer 13, the precursor adsorption density of the ALD film is further improved. Therefore, the inorganic material added to the UC layer 13 will be described in detail. As an inorganic substance added to the UC layer 13, there exists a metal alkoxide (precursor of an inorganic compound), and a metal alkoxide is represented by R1(M-OR2) as a general formula. However, R1 and R2 are a C1-C8 organic group, and M is a metal atom. In addition, the metal atom M is Si, Ti, Al, Zr, etc.

When the metal atom M is Si, as a material represented by R1 (Si-OR2), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxy silane, dimethyldimethoxysilane, and dimethyldiethoxysilane.

When the metal atom M is Zr, examples of the material represented by R1 (Zr-OR2) include tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium and tetrabutoxyzirconium.

When the metal atom M is Ti, examples of the material represented by R1 (Ti-OR2) include tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium and tetrabutoxytitanium.

When the metal atom M is Al, examples of the material represented by R 1 (AI-OR 2 ) include tetramethoxyaluminum, tetraethoxyaluminum, tetraisopropoxyaluminum and tetrabutoxyaluminum.

(Adhesive layer)

The adhesion layer 15 is a layer containing an organic polymer provided on the surface of the UC layer 13 (in other words, between the UC layer 13 and the ALD film 12), as shown in FIG. 4 . In the adhesion layer 15, the functional groups of the organic polymer contained in the UC layer 13 (that is, nucleophilic functional groups such as OH groups and COOH groups) are higher in density than the UC layer 13, and the ALD film 12 It is installed in order to increase the density in which the precursor, which is a raw material of the , cross-links to the functional group.

Specifically, in the adhesion layer 15, at least one of the element ratio O/C of the oxygen element O in the film to the carbon element C or the element ratio N/C of the nitrogen element N in the film to the carbon element C is the UC layer. (13) is a larger surface layer than the inside.

Here, the element ratio of the adhesion layer 15 and the UC layer 13 can be obtained by measuring the peak intensity using X-ray photoelectron spectroscopy (eg, manufactured by Nippon Electronics), and using the ratio of the peak heights. there is. That is, the interface between the adhesion layer 15 and the UC layer 13 can be identified from the element ratio of the adhesion layer 15 and the UC layer 13 .

Specifically, when an element ratio O/C is used, a region in which the element ratio O/C is in the range of 0.45 or more and 0.85 or less from the surface layer portion of the adhesive layer 15 toward the film thickness direction is used as the adhesive layer 15 . It is preferable to do Further, when the element ratio O/C is obtained in the film thickness direction from the bottom of the UC layer 13 toward the surface layer portion, the region in which the element ratio O/C increases by 0.1 or more with respect to the bottom of the UC layer 13 is in close contact. It is preferable to set it as the interface of the layer 15 and the UC layer 13.

On the other hand, when using the element ratio N/C, the adhesion layer 15 is a region where the element ratio N/C is in the range of 0.01 or more and 0.20 or less from the surface layer portion of the adhesion layer 15 toward the film thickness direction. desirable.

In addition, when the element ratio N/C is calculated|required in the film thickness direction from the bottom surface of the UC layer 13 toward the surface layer part, the area|region where element ratio N/C increases 0.02 or more, the adhesive layer 15 and the UC layer 13 ) is preferred.

In addition, in the laminated body 11 after manufacture, it does not specifically limit as a method of confirming the interface of the contact bonding layer 15 and the contact bonding layer 15, and the UC layer 13. Specifically, for example, from the ALD film 12 side or the substrate (polymer substrate) 14 side, the adhesion layer 15 and The presence of an interface can be confirmed.

Moreover, the film thickness of the adhesive layer 15 is although it does not specifically limit, It is preferable that they are 0.1 nm or more and 100 nm or less, It is more preferable that they are 0.3 nm or more and 30 nm or less, It is still more preferable that they are 0.5 nm or more and 10 nm or less. Here, if the film thickness of the adhesion layer 15 is less than 0.1 nm, since there is not more than one atomic layer of nucleophilic functional group and it does not function as an adhesion layer, it is unpreferable. On the other hand, when the film thickness exceeds 100 nm, the surface organic polymer of the UC layer 13 depolymerizes due to long-term treatment, which is not preferable because durability is lowered. On the other hand, if the film thickness of the adhesion layer 15 is in the said range, since it has sufficient nucleophilic functional group and also has durability, it is preferable.

(ALD film)

Specifically as the ALD film 12 , for example, _{an inorganic oxide film such as AlO x} , TiO _x , SiO _x , ZnO _x , SnO _x , a nitride film containing these inorganic substances, an oxynitride film, an element different from these films an oxide film, a nitride film, and an oxynitride film containing Among them, it is preferable that Al, Si, or Ti is included in the ALD film 12 . In addition, the ALD film 12 may be the above-mentioned film or a mixed film of elements.

In addition, although the film thickness of the ALD film|membrane 12 is not specifically limited, It is preferable that they are 2 nm or more and 50 nm or less. Here, when the film thickness of the ALD film 12 is less than 2 nm, the WVTR is about 10 ^-1 , which ^{is not preferable because the target barrier property of 10 -3} or less cannot be obtained. On the other hand, when the film thickness exceeds 50 nm, it is undesirable because it takes cost and time. On the other hand, if the film thickness of the ALD film 12 is within the above range, it is preferable because it can have sufficient water vapor barrier properties for a short time.

<The manufacturing method of the laminated body which concerns on 2nd Embodiment>

Next, the manufacturing method of the laminated body 11 which concerns on 2nd Embodiment of this invention is demonstrated. Here, in the manufacturing method of the laminate 11 according to the embodiment of the present invention, an atomic layer deposition film is laminated on a substrate of a polymer film by an atomic layer deposition method. Specifically, first, the substrate 14 containing the polymer material is loaded in the vacuum chamber of the ALD apparatus (first step). Next, a film-like or film-like UC layer 13 containing an organic polymer is formed on at least a part of the outer surface of the substrate 14 (second step). Next, in the thickness direction of the UC layer 13 formed in the second step, at least a part of the surface (exposed surface of the UC layer 13 ) on the opposite side to the surface in contact with the substrate 14 is surface-treated, and the UC layer 13 ) by introducing a nucleophilic functional group to form the adhesion layer 15 (third step). Next, the precursor raw material is supplied on the surface of the adhesion layer 15 so that the precursor, which is the raw material of the atomic layer deposition film, binds to the functional group of the organic polymer contained in the UC layer 13 or the nucleophilic functional group of the adhesion layer 15 . do (fourth step). Next, in the fourth step, the excess precursor raw material that is not bound is removed, and the amount of the precursor bound to the functional group of the organic polymer contained in the UC layer 13 and the nucleophilic functional group of the adhesion layer 15 is saturated. , an ALD film 12 is formed (fifth step).

The second process WHEREIN: The method of forming the UC layer 13 is not specifically limited, A suitable coating technique, such as a spin coating method, a roll coating method, and a bar coating method, can be used.

3rd process WHEREIN: As a method of surface-treating a part of the surface of UC layer 13, plasma processing (plasma etching), corona treatment, alkali treatment, etc. are mentioned. Thereby, the adhesive layer 15 containing nucleophilic functional groups, such as an OH group and a COOH group, is expressed on a part of the surface of the UC layer 13.

As a result, the density at which the precursor, which is a raw material of the ALD film 12 formed in the fourth and fifth steps, cross-links to the functional group of the adhesion layer 15 or the UC layer 13 increases. As described above, by introducing the adhesive layer 15 in which the functional groups of the organic polymer contained in the UC layer 13 have been densified between the UC layer 13 and the ALD film 12, the gas barrier property of the laminate 11 is improved. can be made even higher.

In the fourth and fifth steps, an atomic layer deposition method (ALD method) is used as a method for forming the ALD film 12 . A precursor raw material (source gas) is supplied, and a purge gas is supplied to remove excess precursor material. It is thought that the precursor is not bonded to some of the nucleophilic functional groups, such as OH group and COOH group, which can react only by supplying and removing the precursor raw material once. Therefore, the ALD film 12 is formed by repeating the step of supplying the precursor raw material and the step of evacuating and removing the surplus precursor raw material to saturate the amount of the precursor bound to the nucleophilic functional group of the organic polymer. It is preferable that the frequency|count of supply and exhaustion of a precursor raw material is 1 or more and 30 or less times.

As described above, according to the manufacturing method of the laminate 11 according to the embodiment of the present invention, after the UC layer 13 is introduced on the polymer substrate 14 and before the ALD film 12 is formed, Since the adhesion layer 15 is provided on the surface layer portion of the UC layer 13 by online plasma pretreatment (that is, after the second process, the third process and the fourth process are performed continuously), the adhesion layer 15 There is no fear that a functional group with high reactivity reacts with a substance in the atmosphere to deactivate it, and there is no fear that the surface of the adhesive layer 15 is contaminated. Thereby, the gas barrier property of the laminated body 11 can be made still higher.

<The gas barrier film according to the second embodiment and the manufacturing method thereof>

A gas barrier film according to an embodiment of the present invention includes the laminate 11 of the above-described form formed in a film shape. Therefore, similarly to the laminate 11 described above, a dense film structure with high gas barrier properties can be obtained.

Moreover, in the manufacturing method of the gas barrier film which concerns on this embodiment, the laminated body 11 manufactured by the manufacturing method of the laminated body 11 mentioned above forms the film form.

As described above, the laminate 11 of the present embodiment has a structure in which the adhesion layer 15 in which functional groups such as C-OH groups and COOH groups are densified is provided on the surface layer of the UC layer 13 . As a result, the density at which the precursor of the ALD film is crosslinked to the functional group of the adhesion layer 15 is increased, so that the gas barrier property of the laminate 11 is further improved. In other words, by providing the adhesion layer 15 in which the functional groups have been densified between the ALD film 12 and the UC layer 13, the density of adsorption sites capable of binding the precursor of the ALD film is increased. Therefore, according to the laminate 11 of this embodiment, the ALD film grows two-dimensionally, and a dense film structure with high gas barrier properties can be obtained.

That is, in the laminate 11 of the present embodiment, the precursor, which is a raw material of the ALD film 12 , can be arranged at a high density at the adsorption site of the adhesion layer 15 , so that atomic layer growth close to two-dimensional growth is possible. The two-dimensionally grown ALD film 12 is a film in which atoms are densely bonded in the plane direction. Therefore, there are few gaps through which gas permeate|transmits in the film thickness direction, and gas barrier property can be made higher. Therefore, it is formed in a film form and can be used as a gas barrier film.

Example

[First embodiment]

Next, specific examples of the laminate of the first embodiment will be described.

(Formation of undercoat layer)

100 μm thick polyethylene terephthalate (PET) film (“A-4100” manufactured by Toyo Bosekki) having one side of the surface treated for easy adhesion and the other side having an untreated surface (hereinafter referred to as “plain surface”). Alternatively, a coating solution is applied using a wire bar on the plain surface of a substrate formed of a 70 µm-thick polypropylene (PP) film (Mitsui Chemical Tocello), and a UC layer having a film thickness of 0.34 µm after drying is formed. laminated.

As a method for producing the coating solution, specifically, first, a copolymer of poly(methacrylic acid-2-hydroxyethyl) and polymethyl methacrylate, poly(methacrylic acid-2-hydroxyethyl) The organic polymer contained in the copolymer in a proportion of 35 mol% was dissolved in a mixed solution of methyl ethyl ketone and cyclohexanone. Then, Smidur N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added to the mixed solution to prepare a coating solution.

Then, the coating liquid was applied to the base material using a wire bar, and it dried at 90 degreeC for 1 minute.

Thereafter, the substrate coated with the coating solution was heated at 60° C. for 48 hours. Thereby, the NCO group of the isocyanate curing agent N3300 and the OH group of at least a part in the poly(methacrylic acid-2-hydroxyethyl) reacted to form a UC layer having the chemical formula shown in FIG. 6 on the substrate.

(Formation of atomic layer deposition film)

_{An Al 2} O ₃ film was formed on the upper surface of the UC layer by an atomic layer deposition method (ALD method). At this time, the raw material gas was made into trimethylaluminum (TMA). In addition, N ₂ and O ₂ was supplied as a purge gas and raw material gas at the same time.

Further, the step of supplying the source gas to the film formation chamber and the step of evacuating and removing the surplus precursor were repeated.

_{Thereafter, O 2} was supplied to the deposition chamber as a reaction gas and discharge gas, respectively. The treatment pressure at that time was 10 to 50 Pa. In addition, a 13.56 MHz power supply was used as a power source for excitation of plasma gas, and plasma discharge was performed in an Inductively Coupled Plasma (ICP) mode.

In addition, the supply time of each gas was 60 msec for TMA and process gas, 10 second for purge gas, and 10 second for reactive gas and discharge gas. Then, while supplying the reaction gas and discharge gas to the film formation chamber, plasma discharge was generated in the ICP mode. In addition, the output power supply of the plasma discharge at this time was set to 250 Watt. Further, as a gas purge after plasma discharge, purge gases O ₂ and N ₂ were supplied to the film formation chamber for 10 seconds. In addition, the film-forming temperature at this time was 90 degreeC.

Deposition rate of Al ₂ O ₃ according to the cycle conditions described above were the same as the following. That is, since the unit film-forming rate was 1.4 to 1.5 angstroms/cycle, 15 cycles of film-forming was performed to form a film with a thickness of 2 nm, and the total time for film-forming was about 1 hour. In order to investigate the influence of the UC layer having an organic polymer containing an OH group on the ALD film, the film thickness of the ALD film was set to 2 nm. By setting the thickness of the ALD film to 2 nm, it is easy to compare the initial growth of the ALD film having a large influence of the UC layer.

(Water vapor transmission rate of the laminate)

Next, about the gas barrier property of a laminated body, the water vapor transmission rate of the laminated body was measured in the atmosphere of 40 degreeC/90%RH using the water vapor transmission rate measuring apparatus (MOCON Permatran (trademark) manufactured by Mocon Corporation). Fig. 7 is a view comparing the water vapor transmission rate of the laminate of the present example and the laminate of the comparative example.

<Example 1>

_{In Example 1, a 2 nm Al 2} O ₃ film was formed on the UC layer on the PET film substrate by the ALD method. The number of times of supply and exhaust of the precursor was set to one. Thus, the water vapor transmission rate (WVTR) was measured about the sample of the produced laminated body. The measured value of WVTR at this time was 4.65 [g/m 2 /day].

<Example 2>

_{In Example 2, a 2 nm Al 2} O ₃ film was formed by the ALD method on the UC layer on the PET film substrate. The supply/exhaust frequency of the precursor was set to 5 times. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 2.27 [g/m 2 /day].

<Example 3>

_{In Example 3, a 2 nm Al 2} O ₃ film was formed on the UC layer on the PET film substrate by the ALD method. The supply/exhaust frequency of the precursor was set to 10 times. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 1.25 [g/m 2 /day].

<Example 4>

_{In Example 4, a 2 nm Al 2} O ₃ film was formed on the UC layer on the PET film substrate by the ALD method. The supply/exhaust frequency of the precursor was set to 15 times. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 1.24 [g/m 2 /day].

<Example 5>

_{In Example 5, before forming the Al 2} O ₃ film on the UC layer on the PET film substrate, plasma discharge was generated in the ICP mode. In addition, the output power supply of the plasma discharge at this time was set to 250 Watt. Further, as a purge gas after the plasma discharge, and supplying a purge gas O ₂ and N ₂ 10 seconds.

When the state of the surface was observed with X-ray photoelectron spectroscopy (manufactured by Nippon Electronics Co., Ltd.), peaks of COOH groups and OH groups were observed, and OH groups on the surface were increased. Then, when the water contact angle of the surface was observed with a contact angle meter (manufactured by KRUSS), it was 43° after plasma treatment compared to 86° before plasma treatment. From this, it turned out that the OH group on the surface was densified by performing a plasma treatment.

_{Thereafter, a 2 nm Al 2} O ₃ film was formed on the surface-treated UC layer by ALD method. The supply/exhaust frequency of the precursor was set to 15 times. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 0.11 [g/m 2 /day].

<Example 6>

_{In Example 6, a 2 nm Al 2} O ₃ film was formed by the ALD method on the UC layer on the PP film substrate. The supply/exhaust frequency of the precursor was set to 5 times. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 2.18 [g/m 2 /day].

<Example 7>

_{In Example 7, a 2 nm Al 2} O ₃ film was formed on the UC layer on the PP film substrate by the ALD method. The supply/exhaust frequency of the precursor was set to 10 times. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 1.29 [g/m 2 /day].

<Example 8>

_{In Example 8, a 2 nm Al 2} O ₃ film was formed on the UC layer on the PP film substrate by the ALD method. The supply/exhaust frequency of the precursor was set to 15 times. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 1.27 [g/m 2 /day].

<Example 9>

_{In Example 9, a 20 nm Al 2} O ₃ film was formed on the UC layer on the PET film substrate by the ALD method. The number of times of supply and exhaust of the precursor was set to one. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 1.0×10 ^-3 [g/m 2 /day].

Next, a comparative example is demonstrated.

<Comparative Example 1>

In Comparative Example 1, a polypropylene (PP) film (manufactured by Mitsui Chemicals Tocell Co., Ltd., a film thickness of 70 μm was regarded as a substrate and a UC layer, and was used as an example as a UC layer having no OH group. Then, Al in this substrate _{WVTR was measured without forming a 2} O ₃ film, and the measured value of WVTR at this time was 4.84 [g/m 2 /day].

<Comparative Example 2>

In Comparative Example 2, similarly to Comparative Example 1, the PP film was regarded as the base material and the UC layer, and was used as the UC layer having no OH group. _{Then, a 2 nm Al 2} O ₃ film was formed on the plane side of the substrate by the ALD method. The supply/exhaust frequency of the precursor was set to 5 times. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 3.24 [g/m 2 /day].

<Comparative Example 3>

In Comparative Example 3, similarly to Comparative Example 1, the PP film was regarded as the substrate and the UC layer, and was used as the UC layer having no OH group. _{Then, a 2 nm Al 2} O ₃ film was formed on the plane side of the substrate by the ALD method. The supply/exhaust frequency of the precursor was set to 10 times. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 2.12 [g/m 2 /day].

<Comparative Example 4>

In Comparative Example 4, similarly to Comparative Example 1, the PP film was regarded as the substrate and the UC layer, and was used as the UC layer having no OH group. _{Then, a 2 nm Al 2} O ₃ film was formed on the plane side of the substrate by the ALD method. The supply/exhaust frequency of the precursor was set to 15 times. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 2.02 [g/m 2 /day].

<Comparative Example 5>

In Comparative Example 5, similarly to Comparative Example 1, the PP film was regarded as the substrate and the UC layer, and was used as the UC layer having no OH group. _{Then, an Al 2} O ₃ film having a thickness of 20 nm was formed on the plane side of the substrate by the ALD method. The number of times of supply and exhaust of the precursor was set to one. WVTR was measured about the sample of the laminated body produced in this way. The measured value of WVTR at this time was 0.30 [g/m 2 /day].

2nm in the Al ₂ O ₃ Example 1 from 8 and Comparative Examples from 2 to 4, and Al ₂ O ₃ content of non-film forming in Comparative Example 1 film in Table 1 the deposition film, conducted by the film forming Al ₂ O ₃ film of 20nm Yes Table 2 summarizes the contents of 9 and Comparative Example 5, respectively.

As described above, the laminate having a UC layer having an organic polymer containing an OH group has a lower WVTR compared to a laminate having a UC layer not containing an OH group, and it has been shown that there is an effect of shielding water vapor more.

[Second embodiment]

Next, specific examples of the laminate of the second embodiment will be described.

(Formation of undercoat layer)

100 μm thick polyethylene terephthalate (PET) film (“A-4100” manufactured by Toyo Boseki) having one side of the surface treated for easy adhesion and the other side having an untreated surface (hereinafter referred to as “plain surface”). A coating solution was applied to the plain surface of the base material formed by using a wire bar, and a UC layer having a film thickness of 0.34 µm after drying was laminated.

Specifically, as a method for preparing the coating solution, first, a copolymer of poly(methacrylic acid-2-hydroxyethyl) and polymethyl methacrylate, poly(methacrylic acid-2-hydroxyethyl) The organic polymer contained in the copolymer in a proportion of 35 mol% was dissolved in a mixed solution of methyl ethyl ketone and cyclohexanone. Thereafter, a coating solution was prepared.

Then, the coating liquid was applied to the base material using a wire bar, and the UC layer was formed on the base material by drying at 90 degreeC for 1 minute.

(Formation of an adhesive layer)

_{Either one of O 2} and N ₂ was supplied to the film formation chamber as a reactive gas and discharge gas on the upper surface of the UC layer, respectively. The treatment pressure at that time was 10 to 50 Pa. In addition, the power supply for plasma gas excitation was 13.56 MHz, and plasma discharge was performed for 60 seconds in ICP (Inductively Coupled Plasma) mode. In addition, the output power supply of the plasma discharge at this time was set to 250 Watt. Further, as a gas purge after plasma discharge, purge gases O ₂ and N ₂ were supplied to the film formation chamber for 10 seconds. In addition, the reaction temperature at this time was 90 degreeC.

Here, with respect to the element ratio of the adhesion layer and the UC layer, the peak intensities of C1s and O1s were compared using X-ray photoelectron spectroscopy (manufactured by Nippon Electronics). MgKα ray was used as the X-ray source, the residence time was 100 milliseconds, and the number of integrations was 5 times. Table 3 below is a table comparing the O/C peak height ratio for the laminate of this example and the laminate of the comparative example.

(Formation of atomic layer deposition film)

_{An Al 2} O ₃ film was formed on the upper surface of the adhesion layer by an atomic layer deposition method (ALD method). At this time, the raw material gas was made into trimethylaluminum (TMA). In addition, N ₂ and O ₂ was supplied as a purge gas and raw material gas at the same time.

Further, the step of supplying the source gas to the film formation chamber and the step of evacuating and removing the surplus precursor were repeated.

_{Thereafter, O 2} was supplied to the deposition chamber as a reaction gas and discharge gas, respectively. The treatment pressure at that time was 10 to 50 Pa. In addition, a 13.56 MHz power supply was used as a power source for excitation of plasma gas, and plasma discharge was performed in an Inductively Coupled Plasma (ICP) mode.

In addition, the supply time of each gas was 60 msec for TMA and process gas, 10 second for purge gas, and 10 second for reactive gas and discharge gas. Then, while supplying the reaction gas and discharge gas to the film formation chamber, plasma discharge was generated in the ICP mode. In addition, the output power supply of the plasma discharge at this time was set to 250 Watt. Further, as a purge gas after the plasma discharge, and supplying a purge gas O ₂ and N ₂ in 10 seconds the chamber. In addition, the film-forming temperature at this time was 90 degreeC.

Deposition rate of Al ₂ O ₃ according to the cycle conditions described above were the same as the following. That is, since the unit film-forming rate was 1.4 to 1.5 angstroms/cycle, 15 cycles of film-forming was performed to form a film with a thickness of 2 nm, and the total time for film-forming was about 1 hour. In order to investigate the influence of the adhesive layer having a nucleophilic functional group on the ALD film, the thickness of the ALD film was set to 2 nm. By setting the thickness of the ALD film to 2 nm, it is easy to compare the initial growth of the ALD film having a large influence of the UC layer.

(Water vapor transmission rate of the laminate)

Next, about the gas barrier property of a laminated body, the water vapor transmission rate of the laminated body was measured in the atmosphere of 40 degreeC/90%RH using the water vapor transmission rate measuring apparatus (MOCON Permatran (trademark) manufactured by Mocon Corporation). Table 4 below is a table comparing the water vapor transmission rate of the laminate of the present example and the laminate of the comparative example.

<Example 10>

In Example 10, plasma treatment was performed for 60 seconds while supplying _{O 2 on the UC layer, and the adhesion layer was introduced.} The element ratio on the surface of the adhesion layer at this time was measured by X-ray photoelectron spectroscopy. The element ratio of O and C of the adhesion layer at this time was O/C=0.68.

_{Then, a 2 nm Al 2} O ₃ film was formed on the adhesion layer by the ALD method. The number of times of supply and exhaust of the precursor was set to 15 times. The water vapor transmission rate (WVTR) was measured about the sample of the laminated body produced in this way. The WVTR at this time was 0.09 [g/m 2 /day].

<Example 11>

In Example 11, plasma treatment was performed for 120 seconds while supplying _{O 2 on the UC layer, and the adhesion layer was introduced.} The element ratio on the surface of the adhesion layer at this time was measured by X-ray photoelectron spectroscopy. The element ratio of O and C of the adhesion layer at this time was O/C=0.72.

_{Then, a 2 nm Al 2} O ₃ film was formed on the adhesion layer by the ALD method. The number of times of supply and exhaust of the precursor was set to 15 times. WVTR was measured with respect to the sample of the laminated body produced in this way. The WVTR at this time was 0.20 [g/m 2 /day].

<Example 12>

In Example 12, plasma treatment was performed for 60 seconds while supplying _{N 2 on the UC layer, and the adhesion layer was introduced.} The element ratio on the surface of the adhesion layer at this time was measured by X-ray photoelectron spectroscopy. The element ratio of N and C in the adhesion layer at this time was N/C=0.03.

_{Then, a 2 nm Al 2} O ₃ film was formed on the adhesion layer by the ALD method. The number of times of supply and exhaust of the precursor was set to 15 times. WVTR was measured with respect to the sample of the laminated body produced in this way. The WVTR at this time was 0.70 [g/m 2 /day].

<Comparative Example 6>

In Comparative Example 6, no surface treatment was performed on the UC layer. The element ratio of the surface of the UC layer at this time was measured by X-ray photoelectron spectroscopy. The element ratio of O and C of the UC layer at this time was O/C=0.40.

_{Then, a 2 nm Al 2} O ₃ film was formed on the adhesion layer by the ALD method. The number of times of supply and exhaust of the precursor was set to 15 times. WVTR was measured with respect to the sample of the laminated body produced in this way. The WVTR at this time was 1.20 [g/m 2 /day].

As described above, it was shown that the laminates of Examples 10 to 12 having the adhesion layer had a lower WVTR than the laminate of Comparative Example 6 not including the adhesion layer, and had an effect of more shielding water vapor.

In addition, although the effect of this invention was demonstrated using an Example and a comparative example in the above, this invention is not limited to the Example etc. mentioned above.

Of course, the laminate of the present invention can be used for electronic components such as electroluminescent elements (EL elements), liquid crystal displays, and semiconductor wafers, but can also be effectively used for packaging films such as pharmaceuticals and foodstuffs.

1, 11: Laminate
2, 12: atomic layer deposition film (ALD film)
3, 13: undercoat layer (UC layer)
4, 14: polymer substrate (substrate)
15: adhesion layer

Claims (15)

a substrate having a surface;
A first organic polymer formed on at least a part of the surface of the substrate, having an OH group, and consisting only of a copolymer of poly(methacrylate-2-hydroxyethyl) and polymethyl methacrylate, is a part of the OH group A film-type or film-type undercoat that is crosslinked intermolecularly through reaction with the NCO group of the second organic polymer containing an NCO group, and a three-dimensional network structure having the OH groups excluding some of the crosslinked OH groups is formed floor and
An atomic layer deposition film formed using a precursor as a raw material and formed in a film shape covering the exposed surface of the undercoat layer
to provide
At least a part of the precursor is bonded to the OH group of the first organic polymer. According to claim 1,
A laminate in which poly(methacrylic acid-2-hydroxyethyl) of the copolymer is contained in a proportion of 15 mol% or more and 50 mol% or less in the copolymer. A polymer substrate having a surface,
a film-like or film-like undercoat layer formed on at least a part of the surface of the polymer substrate and containing an organic polymer;
It is formed so as to cover the surface of the undercoat layer, contains a nucleophilic functional group, and at least one of the element ratio O/C of the oxygen element O and the carbon element C and the element ratio N/C of the nitrogen element N and the carbon element C is an adhesive layer larger than the undercoat layer;
an atomic layer deposition film formed so as to cover the surface of the adhesion layer using a precursor as a raw material;
The adhesion layer becomes a region in which the element ratio O/C is in the range of 0.45 or more and 0.85 or less from the surface layer portion of the adhesion layer toward the film thickness direction, and the element ratio O/C is 0.1 with respect to the bottom surface of the undercoat layer The area increasing abnormally is made the interface between the adhesion layer and the undercoat layer, or
The adhesion layer becomes a region in which the element ratio N/C is in the range of 0.01 or more and 0.20 or less from the surface layer portion of the adhesion layer toward the film thickness direction, and the element ratio N/C is 0.02 with respect to the bottom surface of the undercoat layer. The region that increases abnormally is made the interface between the adhesion layer and the undercoat layer,
The film thickness of the adhesive layer is 0.1 nm or more and 100 nm or less,
At least a part of the precursor is bonded to the nucleophilic functional group. The laminate according to claim 3, wherein the undercoat layer has an element or a functional group containing a lone pair of electrons. The laminate according to claim 3 or 4, wherein the undercoat layer has a film thickness of 100 nm or more and 100 µm or less. The laminate according to claim 3 or 4, wherein the atomic layer deposition film has a thickness of 2 nm or more and 50 nm or less. The laminate according to claim 3 or 4, wherein the atomic layer deposition film contains at least one of Al and Si. The laminate according to claim 3 or 4, wherein the atomic layer deposition film contains Ti on a surface in contact with the adhesion layer. A gas barrier film comprising the laminate according to any one of claims 1 to 4 formed in a film shape. prepare the material,
A first organic polymer having a functional group containing an OH group on at least a part of the surface of the substrate and consisting only of a copolymer of poly(methacrylic acid-2-hydroxyethyl) and polymethyl methacrylate, A film-type or film-type under which is crosslinked intermolecularly through a reaction between a part and the NCO group of the second organic polymer containing an NCO group, and a three-dimensional network structure having the OH groups excluding the crosslinked part of the OH group is formed coat layer,
A portion of the exposed surface of the undercoat layer is surface-treated to densify the functional groups of the first organic polymer,
supplying a precursor raw material on the exposed surface so that the precursor serving as the atomic layer deposition film binds to the OH group and the densified functional group of the first organic polymer contained in the undercoat layer,
An atomic layer deposition film is formed by removing an excess of the precursor raw material that is not bound to the undercoat layer in the precursor raw material, and saturating the amount of binding of the precursor to the OH group and the densified functional group of the first organic polymer. doing
A method for manufacturing a laminate comprising prepare the material,
Forming a film-like or film-like undercoat layer containing an organic polymer having a functional group on at least a part of the surface of the substrate,
forming an adhesive layer having a nucleophilic functional group on the undercoat layer with a film thickness of 0.1 nm or more and 100 nm or less by surface treatment of at least a part of the exposed surface of the undercoat layer;
The adhesion layer becomes a region in which the element ratio O/C is in the range of 0.45 or more and 0.85 or less from the surface layer portion of the adhesion layer toward the film thickness direction, and the element ratio O/C is 0.1 with respect to the bottom surface of the undercoat layer The area increasing abnormally is made the interface between the adhesion layer and the undercoat layer, or
The adhesion layer becomes a region in which the element ratio N/C is in the range of 0.01 or more and 0.20 or less from the surface layer portion of the adhesion layer toward the film thickness direction, and the element ratio N/C is 0.02 with respect to the bottom surface of the undercoat layer. The region that increases abnormally is made the interface between the adhesion layer and the undercoat layer,
A precursor raw material is supplied on the surface of the adhesion layer so that the precursor serving as the atomic layer deposition film binds to a functional group of the undercoat layer or a nucleophilic functional group of the adhesion layer,
In the precursor raw material, the excess of the precursor raw material not bonded to the undercoat layer and the adhesion layer is removed, and the amount of binding of the precursor bound to the functional group of the undercoat layer or the nucleophilic functional group of the adhesion layer is saturated, forming an atomic layer deposition film
A method for manufacturing a laminate comprising The manufacturing method of the gas barrier film which forms a laminated body in film form by the manufacturing method of the laminated body of Claim 10 or 11. delete delete delete

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